You cannot compare SPI and RS-232. One is an interface protocol and the latter is an electrical standard.
RS-232 was designed for device to device communications over moderate distances, approximately 10 m max, for example, between computers and printers, modems, etc. It defines the voltage, current, rise and fall times, and high voltage tolerance. RS-485 can be used over longer distances.
If you meant UART TTL interface, it would be limited to similar restrictions as SPI.
SPI and TTL interfaces are intended for chip to chip communications for no more that a few centimetres on the same board.
By the way, you can send SPi over RS-232 standard.